Olefin conversion using complexes of cu,ag and au with organoaluminums

ABSTRACT

A PROCESS FOR THE CONVERSION OF OLEFINIC HYDROCARBONS ACCORDING TO THE OLEFIN REACTION (E.G., THE OLEFIN DISPROPORTIONATION REACTION) BY CONTACTING THE OLEFINIC HYDROCARBON WITH A CATALYST COMPRISING A COORDINATION COMPLEX OF COOPER, SILVER, OR GOLD TOGETHER WITH AN ALUMINUMCONTAINING ADJUVANT.

United States Patent Ofice 3,703,561 OLEFIN CONVERSION USING COMPLEXES FCu, Ag AND An WITH ORGANOALUMINUMS Donald H. Kubicek and Ernest A.Zuech, Bartlesville, Okla, assignors to Phillips Petroleum Company NoDrawing. Application Mar. 28, 1968, Ser. No. 717,024, now Patent No.3,558,520, dated Jan. 26, 1971, which is a continuation-in-part ofabandoned application Ser. No. 635,693, May 3, 1967. Divided and thisapplication Sept. 17, 1970, Ser. No. 73,233

Int. Cl. C07c 3/62 US. Cl. 260-683 D 11 Claims ABSTRACT OF THEDISCLOSURE A process for the conversion of olefinic hydrocarbonsaccording to the olefin reaction (e.g., the olefin disproportionationreaction) by contacting the olefinic hydrocarbon with a catalystcomprising a coordination complex of copper, silver, or gold togetherwith an aluminumcontaining adjuvant.

This application is a division of copending application Ser. No.717,024, filed Mar. 28, 1968, now Pat. No. 3,558,520, which is acontinuation-in-part of copending application Ser. No. 635,693, filedMay 3, 1967, now abandoned.

This invention relates to the conversion of olefins and to a homogeneouscoordination complex catalyst for such conversion. In one aspect, thisinvention relates to the olefin reaction. In another aspect, it relatesto the conversion of olefins to other olefins having different molecularweights. In still another aspect, it relates to a novel homogeneous,coordination complex catalyst system.

The term olefin reaction, as used herein, is defined as a process forthe catalytic conversion over a catalyst of a feed comprising one ormore ethylenically unsaturated compounds to produce a resulting productwhich contains at least ten percent by weight of product compounds,which product compounds can be visualized as resulting from at least oneprimary reaction, as defined below, or the combination of at least oneprimary reaction and at least one unsaturated bond isomerizationreaction, and wherein the sum of compounds contained in said resultingproduct consisting of hydrogen, saturated hydrocarbons, and compoundswhich can be visualized as formed by skeletal isomerization but whichcannot be visualized as formed by one or more of the above-notedreactions, comprises less than twenty-five percent by weight of thetotal of said resulting product. Feed components and unsaturated bondisomers thereof are not included in the resulting product for thepurpose of determining the above-noted percentages.

-In the olefin reaction, as defined above, the primary reaction is areaction which canbe visualized as comprising the breaking of twoexisting unsaturated bonds between first and second carbon atoms andbetween third and fourth carbon atoms, respectively, and the formationof two new saturated bonds. Said first and second carbon atoms and saidthird and fourth carbon atoms can be in the same or different molecules.

The olefin reaction according to this invention is illustrated by thefollowing reactions:

3,703,561 Patented Nov. 21, 1972 (1) The disproportionation of anacyclic monoor polyene having at least three carbon atoms into otheracyclic monoor polyenes of both higher and lower number of carbon atoms;for example, the disproportionation of propylene yields ethylene andbutenes; the disproportionation of 1,5-hexadiene yields ethylene and1,5,9-decatriene;

(2) The conversion of an acyclic monoor polyene having three or morecarbon atoms and a different acyclic monoor polyene having three or morecarbon atoms to produce different acyclic olefins; for example, theconversion of propylene and isobutylene yields ethylene and isopentene;

(3) The conversion of ethylene and an internal acyclic monoor polyenehaving four or more carbon atoms to produce other olefins having a lowernumber of carbon atoms than that of the acyclic monoor polyene; forexample, the conversion of ethylene and 4-methylpentene-2- yields3-methylbutene-1 and propylene;

(4) The conversion of ethylene or an acylic monoor polyene having threeor more carbon atoms and acyclic monoor cyclic polyene to produce anacyclic polyene having a higher number of carbon atoms than that of anyof the starting materials; for example, the conversion of cycloocteneand Z-pentene yields, 2,10-tridecadiene; the conversion of1,5-cyclooctadiene and ethylene yields 1,5, 9-decatriene;

(5) The conversion of one or more cyclic monoor cyclic polyenes toproduce a cyclic polyene having a higher number of carbon atoms than anyof the starting materials; for example, the conversion of cyclopenteneyields 1,6-cyclodecadiene, and continued reaction can produce stillhigher molecular weight materials;

(6) The conversion of an acyclic polyene having at least seven carbonatoms and having at least five carbon atoms between any two double bondsto produce acyclic and cyclic monoand polyenes having a lower number ofcarbon atoms than that of the feed; for example, the conversion of1,7-octadiene yields cyclohexene and ethylene; or

(7) The conversion of one or more acyclic polyenes having at last threecarbon atoms between any two double bonds to produce acyclic and cyclicmonoand polyenes generally having both a higher and lower number ofcarbon atoms than that of the feed material; for example, the conversionof 1,4-pentadiene yields 1,4-cyclohexadiene and ethylene.

New catalytic processes have been discovered, in recent years, for theconversion of olefins to other olefinic products including products ofboth higher and lower molecular weight whereby olefins of relatively lowvalue are converted into olefins of higher value. Such conversions havebeen carried out with heterogeneous catalysts such as those comprisingcompounds of metals such as molybdenum or tungsten which are usuallyassociated with solid support materials such as alumina or silica. Ithas now been found that these olefin conversions can be carried out in asubstantially homogeneous state using, as catalysts, selectedcoordination complexes of copper, silver or gold in combination withsuitable organo metal catalytic adjuvants to produce olefins ofincreased value including solid products, for example, rubber suitablefor the manufacture of tires, wire coating, footwear and otherindustrial products.

It is an object of this invention to provide a method and a homogeneouscatalyst system for the conversion of olefin hydrocarbons. It is also anobject of this invention to provide a homogeneous catalyst comprising acoordination complex of copper, silver or gold, together with analuminum containing catalytic adjuvant for the olefin reaction. Stillanother object is to provide a method for converting olefins to otherolefins according to the olefin reaction. The provision of a homogeneouscoordination catalyst of copper, silver or gold together with analuminum-containing catalytic adjuvant for converting olefins to otherolefins of higher and lower number of carbon atoms is yet another objectof this invention. Other aspects, objects and advantages of theinvention will be apparent to one skilled in the art upon study of thedisclosure including the detailed description of the invention.

According to the process of this invention, olefinic compounds areconverted to other olefinic compounds by contact under conditionssuitable to disproportionate an olefin into other olefins having higherand lower number of carbon atoms, with a catalyst system which forms onadmixing, under catalyst formation conditions, components comprising:

(a) The copper, silver, or gold-containing reaction product formed bythe admixture of a copper, silver, or gold compound, such as a salt ofan organic acid having up to 20 carbon atoms or an inorganic acid,preferably a halogen acid, with at least one complexing agentrepresented by the formula: R Q, R QO, R QQR CO,

NO, NOX,

RDU

radical-containing compounds, RCOCH COR, RNR R N-R -NR R (COOH) (CHR'=CR CH radical-containing compounds; or

wherein each R is a saturated aliphatic or aromatic hydrocarbon radical,including alkoxyand halo-substituted radicals, having up to 20 carbonatoms; Q is phosphorus, arsenic, or antimony; R is hydrogen or R; R is adivalent saturated aliphatic or aromatic hydrocarbon radical having upto 20 carbon atoms; R is a divalent saturated or ethylenicallyunsaturated hydrocarbon radical having from 3 to carbon atoms; R ishydrogen or a methyl radical; h is 0, 1, 2 or 3; m is l or 2; R is anaromatic, saturated aliphatic, or ethylenically unsaturated aliphatichydrocarbon radical having up to carbon atoms; n is 0-5; X is a halogen,with (b) A catalytic adjuvant selected from (2) a mixture of (1)compounds,

(3) a mixture of one or more R AlX or AlX compounds with one or morecompounds represented by the formula R M X or (4) a AlX compound,

wherein each R is a saturated aliphatic or aromatic organic radical,including alkoxyand halo-substituted radicals, having up to 20 carbonatoms, preferably an alkyl radical having up to 10 carbon atoms; each Xis a halogen; each M is a metal of Group I-A, II-A, II-B, or III-A; eachR is selected from hydrogen or R; a is 1,2or3,bis0,1or2,thesumofaandbbeing3;cis1, 2 or 3, d is 0, 1 or 2, the sumof c and d being equal to the valence of M and when the adjuvant is (1)and acyclic olefins are converted, b is preferably 1 or 2.

The Group I-A, II-A, II-B, and III-A metals are referred to as in thePeriodic Table of Elements appearing in Handbook of Chemistry andPhysics, Chemical Rubber Co., 45th Edition (1964), page B-2.

Some examples of compounds of R AlX and AlX compounds are methylaluminumdichloride, dimethylaluminum fluoride, methylaluminum sesquichloride,ethylaluminum dichloride, ethylaluminum sesquichloride, aluminumtrichloride, di(2-ethylhexyl)aluminum bro mide, phenylaluminumdichloride, aluminum tribromide, di(3-ethoxypropyl)aluminum bromide,benzylaluminum diiodide, dieicosylaluminum bromide, and the like, andmixtures thereof.

Some examples of compounds of the formula R M X are phenyllithium,t-butylpotassium, methylsodium, benzylrubidium, lithium hydride,anthrylcesium, lithium aluminum hydride, ethylberyllium hydride, lithiumboronhydride, methylcadmium chloride, diethylzinc, dicyclohexylmercury,dipropylzinc, triethylaluminum, methylgallium dibromide,trieicosylaluminum, triethylindium, di- (12-chlorododecyl)-aluminumchloride, triisopropylthallium, dimethylcalcium, dirnethylstrontium,diethylbarium, and the like, and mixtures thereof.

The preferred adjuvants, or (b) catalyst components, are (1) or (2).

Some examples of suitable copper, silver, or gold compounds which can beused in the preparation of the (a) component of the present inventionare: Cu Cl Cu Br Cu l Cu F AgCl, AgBr, AgI, AgF, AuCl AuBr,, AuF, AuICuCN, CuSCN, Cu(acetate) Ag laurate, Au stearate, Cu(benzoate) Cu (SnClCu (CN) Au(CN) AuCl, AuBr, AuCN, AgCN, and AgCNS.

Some examples of suitable complexing agents or ligandforming materialsfor use in the present invention are: triphenylphosphine oxide,tetramethyldiphosphine, tetrabenzyldistibine, trimethylphosphine,tri-n-butylphosphine, tri-n-decylphosphine, tri-n-eicosylphosphine,methyldi-noctylphosphine, tricyclohexylphosphine, triphenylphosphine,tribenzylphosphine, triethylarsine, triiisopropylarsine,tri-n-pentadecylarsine, diethyl-n-tridecylarsine, tricyclopentylarsine,tri(4-cyclohexylbutyl)arsine, diethylphenylarsine,tri(3,6-diphenyloctyl)arsine, tri-t-butylstibine, tri-n-nonylstibine,tri(-6,8-di-n-butyldecyl)stibine, tri- (3,5 dimethylcyclohexyl)stibine,methyldicyclohexyl stibine, tri(2,4,6-triethylphenyl)stibine,methyldi(4-dodecylphenyl)stibine, trimethylamine, tri-tert-butylamine,trin-decylamine, trieicosylamine, tricyclohexylamine, triphenylamine,tribenzylamine, ethyldi-n-tridecylamine, diisopropyl-4-tolylamine,tri(6phenylhexyl)amine, tri(3,5- di-n-heptylcyclohexyl)amine, andisopropyldiphenylamine; sodium cyclopentadienylide, lithium2-methylcyclopentadienylide, NO, NOCl, NOI, NOBr, NOF, cyclopentylamine,dibutylamiue, N,N,N,N'-tetramethylethylenediamine,N,N-dibenzylethylcnediamine, 3-(diethylamino) propylamine,4-vinylpyridine, pyridine, 4-(2-ethylhexyl) pyridine, 2,2'-bipyridyl,butyl sulfide, phenyl sulfide, thiophene, 2,5-diethylthiophene, allylbromide, methallyl chloride, crotyl iodide,tetrakis(2-methyl-2-butenyl)tin, tetramethallyltin, tetraallyltin,acetic acid, oxalic acid, benzoic acid, malonic acid, lauric acid,acetylacetone, 1,3- diphenyl-1,3-propanedione, and the like, andmixtures thereof.

Some I-B metal containing coordination complexes which can be used ascomponent (a) of the invention can be represented by the formula [(L),,MZ wherein M is copper, silver or gold; each Z is halogen, SnCl CN, SCN,or a carboxylic acid radical having up to 20 carbon atoms per molecule;and each (L) is selected from aQ aQ zQQ z R R-S-R, 1535 \N n coo-'(QHEICEECHB), and

e is 1-5; 1 is generally 1 but can be 2 or higher particularly when M iscopper; g is 1-6; and the number of (L) and Z groups present in thecomplex is not greater than the number required for the metal to achievethe closed shell electronic configuration of the next higher atomicnumber inert gas; x is a number representing the polymeric state of thecomplex and is generally 1, 2 or 3; and wherein h, m, Q, R, R R R R, Rand n are as defined earlier.

Some examples of complexes which are suitable for use as component (a)are:

(triphenylphosphineoxide) Cu Cl (triphenylphosphine Cu Cltriphenylphosphine )AuCl,

[ (triphenylphosphine) AgBr] (tributylphosphine) Cu Cltricyclohexylstibine) Cu Cl- (tribenzylarsine Cu Br tridodecylphosphine)AuCl, [tri (Z-ethylhexyl stibine] AuI, ['(tricyclopentylasrsine) AgCl](pyridine) CuB r (m-toluidine) CuBr (aniline) CuCI o-phenylenediamineCuCl- (pyridine Cu Cl (triphenylphosphine AuCl (triphenylstibine )AuCl,(triphenylphosphine) Au CN, (pyridine) (triphenylphosphine) AgCl,(triphenylphosphine) AgCl, (triphenylphosphine AgI,

and the like, and mixtures thereof.

The formula [(L),,M;Z is used herein to identify the product obtained byadmixture of copper, silver or gold compound with at least onecomplexing agent. Thus, if the metal compound is gold chloride and thecomplexing agent is triphenylphosphine, the reaction product isconsidered to be triphenylphosphine gold chloride. It should beunderstood, however, that the catalytic agent which has activity for theolefin reaction conversion is the product resulting from the admixtureof the metal compound and the complexing agent, and thealuminum-containing compound whether or not the components are presentin the complex as indicated in the formula.

The (a) component of the catalyst system is the product obtained bycombining a copper, gold, or silver compound with 1 or more suitableligand-forming materials. These materials are simply combined underconditions of time and temperature which permit the complex to beformed. In general, excessively high temperatures at which the reagentstend to decompose, or excessively low temperatures, at which thereagents tend to crystallize or otherwise tend to become unreactive,should be avoided. The molar proportion of transition metal salt to theselected ligandformer can be in the range of from about 0.1:1 to about10: 1, preferably from about 0.5 :1 to about 2:1. The products areobtained by combining these ingredients at a temperature preferably inthe range of from about to about 130 C., more preferably 0 to about 60C., for a time in the range of from a few seconds up to about 24 hours,preferably in the presence of a diluent in which the components of theadmixture are at least partially soluble. Any convenient diluent such ascarbon tetrachloride, methylene chloride, xylene, cyclohexane,isooctane, benzene, chlorobenzene, and the like, can be used for thispurpose. Any order of addition can be used. Such product need not beisolated but the mixture can be used directly in the formation of thecatalyst system. In general, the (a) component of the catalyst system isfully prepared before contact is made with the (b) component oradjuvant.

The molar proportion of the (b) component to the (a) component, to formthe catalyst system of the present invention, will generally be in therange of from about 0.1:1 to 20:1, preferably from about 1:1 to about10:1.

The catalyst is prepared simply by combining the (a) component and the(b) component under conditions of time and temperature which permit thecatalytically active mixture to be formed, avoiding excessively hightemperatures at which some of the reagents tend to decompose orexcessively low temperatures at which some of the reagents tend tocrystallize or otherwise tend to become inactive. This combinationoccurs very readily and, in general, the components can be mixed at anyconvenient temperature preferably within the range of to about 0.,preferably 0 to 60 C., for a few seconds or for several hours in thepresence of a diluent in which both the components are at leastpartially soluble. Any convenient diluent such as benzene, cyclohexane,toluene, chlorobenzene, methylene chloride, ethylene chloride, and thelike, can be used for this purpose. Halogenated diluents are generallypreferred. The mixing of the two catalyst components is carried out inthe substantial absence of air or moisture, generally in an inertatmosphere. After the catalytic reaction mixture is formed, it need notbe isolated but can be added directly to the olefin reaction zone as adispersion in its preparation solvent. If desired, the catalystcomponents can be separately added, in any order, to the reaction zone,either in the presence or absence of the feed olefin.

Olefins applicable for use in the process of the invention arenon-tertiary, non-conjugated, acyclic monoand polyenes having at least 3carbon atoms per molecule including cycloalkyl, cycloalkenyl, and arylderivatives thereof; cyclic monoand polyenes having at least 4 carbonatoms per molecule including alkyl and aryl derivatives thereof;mixtures of the above olefins; and mixtures of ethylene and the aboveolefins. Many useful reactions are accomplished with such acyclicolefins having 3-30 carbon atoms per molecule and with such cyclicolefins having 4-30 carbon atoms per molecule. Non-tertiary olefins arethose olefins wherein each carbon atom, which is attached to anothercarbon atom by means of a double bond, is also attached to at least onehydrogen atom.

Some specific examples of acyclic olefins suitable for reactions of thisinvention include propylene, l-butene, 2- butene, l-pentene, 2-pentene,l-hexene, 1,4-hexadiene, 2- heptene, l-octene, 2,5-octadiene, 2-nonene,l-dodecene, 2- tetradecene, l-hexadecene, 1-phenylbutene-2, 4-octene, 3-eicosene, 3-hexene, 1,4-pentadiene, 1,4,7-dodecatriene, 4-

.methyl-4-octene, 4-vinylcyclohexene, 1,7-octadiene, 1,5-

eicosadiene, Z-triacontene, 2,6-dodecadiene, l,4,7,10,13-octadecapeutaene, 8-cyclopentyl-4,S-dimethyl-1-decene, 6,6-dimethyl-1,4-octadiene, and 3-heptene, and the like, and mixturesthereof.

Some specific examples of cyclic olefins suitable for the reactions ofthis invention are cyclobutene, cyclopentene, cycloheptene, cyclooctene,S-n-propylcyclooctene, cyclodecene, cyclododecene, 3,3,5,5tetramethylcyclononene, 3,4,5,6,7-pentaethylcyclodecene,1,5-cyclooctadiene, 1,5,9- cyclododecatriene,1,4,7,l0-cyclododecatetraene, 6-methyl- 6;?ethylcyclooctadiene-1,4, andthe like, and mixtures there- 0 It will be understood by those skilledin the art that not all olefinic materials will be converted by thepresent invention with equal effectiveness. The reactions described inthe present invention are equilibrium-limited reactions and, barring theselective removal of one or more products from the reaction zone, theextent of conversion will depend upon the thermodynamics of the specificsystems observed. Thus, conversion of olefinic materials to givespecific products can be thermodynamically favored while the reversereaction is very slow and ineffective. For example, 1,7-octatriene isconverted to equilibrium-favored products such as cyclohexene andethylene. The reverse reaction of ethylene and cyclohexene,correspondingly, goes very poorly. Other well known factors, such asstearic hindrance in bulky molecules, significantly and sometimesdrastically affect the rates of reaction of some olefins such thatextremely long reaction times are required.

The reaction of symmetrical monoolefins with themselves, to givedifferent olefin products, will sometimes proceed very slowly, requiringsome double bond migration to take place before the reaction willproceed at a significant rate. For the same reason, the conversion of amixture of ethylene and a l-olefin, for example, can be more difficultthan the conversion of ethylene with an internal olefin, some doublebond isomerization also being required in this instance.

It has also been found that branching also retards the olefin reactivityin proportion to its propinquity to the reacting double bond.Analogously, the presence of inert polar substituents on the olefiniccompound appears tolerable only if located some distance from the doublebond.

Thus, the present invention is directed primarily to the conversion ofthose olefins or combination of olefins which are capable of undergoingthe olefin reaction to a significant degree when contacted with thecatalyst of the present invention under reaction conditions suitable foreffecting the olefin reaction.

Presently preferred olefinic feed compounds are those contained in thefollowing classes:

(1) Acyclic monoolefins, including those with aryl, cycloalkyl, andcycloalkenyl substituents, having 3 to 20 carbon atoms per molecule withno branching closer than about the 3-position and no quaternary carbonatoms or aromatic substitution closer than the 4-position to the doublebond, and mixtures of such unsubstituted acyclic monoolefins. Someexamples of these are: propylene, pentene-l, pentene-Z, butene-l,butene-2, 3-methylbutene- 1, hexene-2, octene-4, nonene-2,4-methylpentene-1, decene-3, 8-ethyldecene-2, dodecene-4,vinylcyclohexane, 4- vinylcyclohexene, eicosene-l, and the like.

(2) A mixture of ethylene and one or more acyclic unsubstituted internalmonoolefins of (1). Some examples of such mixtures are: ethylene andbutene-2, ethylene and pentene-Z, ethylene and hexene-3, ethylene andheptene-3, ethylene and 4-methylpentene-2, ethylene and octene-4,ethylene and dodecene-4, and the like.

(3) Acyclic, non-conjugated polyenes having from to about carbon atomsper molecule, containing from 2 to about 4 double bonds per molecule andhaving at least one double bond with no branching nearer than the3-position and no quaternary carbon atom nearer than the 4-position tothat double bond, or mixtures of such polyenes. Some examples are:1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, 2,6-decadiene,1,5,9-dodecatriene, 4- methylheptadiene-1,6, 1,7-octadiene,1,6-octadiene, and the like.

(4) A mixture of ethylene and one or more acyclic polyenes of (3) whichcontain at least one internal double bond. Some examples are: ethyleneand 1,6-octadiene, ethylene and 1,5-clecadiene, and the like.

(5) Cyclopentene.

(6) Monocyclic and bicyclic monoolefins having 7 to 12 ring carbonatoms, including those substituted with up to 3 alkyl groups having upto about 5 carbon atoms, with no branching closer than the 3-positionand with no quaternary carbon atoms closer than the 4-position to thatdouble bond, and mixtures of such olefins including mixtures withcyclopentene. Some examples are: cycloheptene, cyclooctene,4-methylcyclooctene, 3-methyl-5- ethylcyclodecene, cyclononene,cyclododecene, norbornene, and the like.

(7) A mixture of one or more of the monocyclic olefins of (6) witheither ethylene or with one or more unsubstituted acyclic monoolefins of(1). Some examples of these are: ethylene and cycloheptene, ethylene andcyclooctene, propylene and cyclodecene, pentene-2 and cyclooctene,ethylene and cyclododecene, and the like.

(8) Monocyclic and bicyclic non-conjugated polyenes having from 5 toabout 12 ring carbon atoms, including those substituted with up to 3alkyl groups having up to about 5 carbon atoms each, having at least onedouble bond with no branching closer than the 3-position and with noquaternary carbon atoms closer than the 4-position to that double bond,and mixtures thereof. Some examples of these are: 1,5-cyclooctadiene,1,5,9-cyclododecatriene, 1,4-cycloheptadiene, norbomadiene, and thelike.

(9) A mixture of one or more monocyclic polyenes of (8) with one or moreacyclic l-olefins having from 2 to about 10 carbon atoms, having nobranching nearer than the 3-position and no quaternary carbon atomsnearer than the 4-position to the double bond. Some examples of theseare: 1,5-cyclooctadiene and ethylene, 1,5,9-cyclododecatriene andethylene, 1,5,9-cyclododecatriene and pentene-l, and the like.

(10) Polar group-substituted olefinic compounds of classes (1) through(9) containing from about 5 to about 20 carbon atoms per molecule inwhich the polar group, such as a halogen atom, is sufficiently removedfrom the active double bond (generally, no nearer to the double bondthan the 5-position) so as not to interfere with the reaction, andmixtures with unsubstituted members of class (1). Some examples are:S-chloropentene-l, a mixture of pentene-2 and S-chloropentene-l, and thelike.

According to the process of the invention, the olefins or mixture ofolefins to be converted is contacted with the catalyst system at anyconvenient temperature, avoiding excessively high temperatures at whichsome of the reagents tend to decompose, or excessively low temperaturesat which some of the reagents tend to crystallize or otherwise tend tobecome inactive. The process will often be carried out at a temperaturepreferably within the range of from about 30 to about 150 C., morepreferably from 0 to about 75 C., at any convenient pressure which issufficient to maintain a liquid phase. The conversion can be carried outin the presence of any diluent such as that used for the catalystpreparation, if desired. Diluents are not essential but are generallypreferred and such di'luents can include saturated aliphatics andaromatics such as cyclohexane, xylene, isooctane and the like, andhalogenated derivatives thereof. The time of contact will depend uponthe desired degree of conversion and the catalysts and olefins utilized,but will, generally, be in the range of from about 0.1 minute to 24hours, preferably 5 to 120 minutes. The proportion of catalystcomposition to olefin feed in the reaction zone will generally be in therange of from about 0.001- millimoles of the Group I-B metal for eachmole of olefin in the reaction zone.

Any conventional contacting technique can be used for the olefinconversion, and batchwise or continuous opera tion can be utilized.After the reaction period, the products can be separated and/or isolatedby conventional means such as by fractionation, crystallization,adsorption, and the like. Unconverted feed material or products not inthe desired molecular weight range can be recycled to the conversionzone. If desired, the catalyst can be destroyed by treatment with asuflicient amount of water or alcohol prior to the separation of theproducts, to inactivate the catalyst. Otherwise, after separation of theproducts, the catalyst can be recycled to the reaction zone. Separationof products can be accomplished by distillation, crystallization,evaporation, and the like.

EXAMPLE I Disproportionation of heptene-Z over {triphenylphosphine)Cugcl /methylaluminum sesquichloride or ethylaluminum dichloride A dry7-oz. pressure bottle was charged with 0.1 g. (tri pheny1phosphine) CuCl and 10 ml. chlorobenzene. The bottle was flushed with nitrogen andthe water-white solution was cooled in an ice-water bath. To this wasadded 0.2 ml. of methylalumin'um sesquichloride and 10 ml. of heptene-2.This reaction mixture was stirred for 2 hours at C. and for anadditional 2 hours at 80 C. After hydrolysis, the reaction mixturecontained the disproportionation products, butene and decene. Theconversion of heptene-2 was about 0.2 percent.

In another similar run in which the methylaluminum sesquichloride wasreplaced by ethylaluminum dichloride, ml. of pentene-2 was contcatedwith 0.05 g. of the same copper compound and 0.2 ml. of ethylaluminumdichloride in 5 ml. chlorobenzene in a 16-hour reaction at roomtemperature. Analysis showed that about 0.6 percent of the pentene-2 wasconverted to the disproportionation products, butene and hexene.

EXAMPLE II Disproportionation of pentene-Z over (triphenylphosphine)AuClmethylaluminum sesquichloride (Triphenylphosphine)AuCl was prepared bythe reaction of AuClwith two equivalents of triphenylphosphine in ethylalcohol.

Into a dry 7-oz. pressure bottle were added 0.05 gram of(triphenylphosphine)AuCl, 5 ml. of ethylene chloride and a magneticstirring bar. The system was flushed with dry nitrogen, 5 ml. ofpentene-2 and 1 ml. of a molar solution of methylaluminum sesquichloridein chlorobenzene were added. The mixture was stirred for 60 hours atroom temperature, hydrolyzed with about an equal volume of Water andanalyzed by G.L.C. (gas-liquid chromatography).

The reaction mixture, excluding ethylene which was vented, was found tocontain 0.7 weight percent butane and 2.2 weight percent hexene.

EXAMPLE III Disproportionation of pentene-2 over[(triphenylphosphine)tAgBr] ethylaluminum dichloride Into a dry 7-oz.pressure bottle were added 0.5 gram of [(triphenylphosphine)AgBr] amagnetic stirrer and 10 ml. of phenyl chloride. The system was flushedwith dry nitrogen and 1 ml. of a 1 molar solution of ethylaluminumdichloride in phenyl chloride was added. The mixture was stirred at roomtemperature for 1 hour and 5 ml. of pentene-2 were added and stirringwas continued for 18 hours. A sample was removed, hydrolyzed, andanalyzed by G.L.C. The chromato'gram showed the presence of butenes andhexene. The remainder of the mixture was stirred for 6 hours at 80 (3.,hydrolyzed and analyzed by G.L.C. More disproportionation products wereindicated.

In the practice of the process of this invention, the feed olefins,catalysts and operating conditions disclosed include combinationswherein solid, rubbery materials are produced; for example, if apropylene feed and a suitable aluminum-containing adjuvant such as anorganoaluminum dihalide or an organoaluminum sesquihalide are used, asolid, rubbery material is produced having characteristics ofethylene-propylene rubber. This rubbery material is useful in themanufacture of tires, wire coating, footwear and other industrialproducts.

The homogeneous catalysts of this invention can be deposited upon asuitable support or carrier and used in the olefin reaction, preferablywhere the olefin feed is in the vapor phase. Catalyst supports includesolid, inorganic or organic materials conventionally used as catalystsupports or carriers such as silica, alumina, silica-alumina, titania,boria, zeolites, ion exchange resins, solid polymers containingfunctional groups such as those prepared by the polymerization of4-vinylpyridine, vinyl dimethylplrosphine, and the like.

The support can be impregnated with the homogeneous catalyst by wettingthe support with a solution of the catalyst in a solvent which is thenevaporated. The support can also be impregnated with either the (a) or(b) component and the remaining component can be added later. Forexample, the solid support material can be impregnated with the (a)component and the resulting composite conveniently stored untilrequired. Just prior to use, the composite can be treated with the (b)component, or, if the reaction is in the liquid phase, the (b) componentcan simply be added to the reaction zone. Among impregnating solventssuitable are relatively low-boiling organic solvents such as pentane,methylene chloride, cyclohexane, and the like. The amount of homogeneouscatalyst added to the support will be from 0.1 to about 30 weightpercent of the total of the catalyst and support. If the support is tobe activated by \calcinatio-n, it is usually activated prior to theimpregnation step.

Impregnation and evaporation conditions in preparing the catalyst areconventional, being carried out at temperatures up to about C. Operatingconditions in carrying out the olefin reaction are the same for thesupported and the nonsupported homogeneous catalyst systems.

We claim:

1. A process for the conversion of olefins selected from the groupconsisting of nontertiary, nonconjugated, acyclic monoand polyeneshaving at least 3 carbon atoms per molecule, including cycloalkyl,cycloalkenyl and aryl derivatives thereof; cyclic monoand polyeneshaving at least 4 carbon atoms per molecule and including alkyl and arylderivatives thereof; mixtures of the above olefins, or mixtures ofethylene and the above olefins, said conversion being in accordance withthe olefin reaction which, as defined herein, can be visualized ascomprising the reaction between two first pairs of carbon atoms, the twocarbon atoms of each first pair being connected by an olefinic doublebond, to form two new pairs from the carbon atoms of said first pairs,the two carbon atoms of each of said new pairs being connected by anolefinic double bond, by contacting said olefins with a catalystconsisting essentially of (a) a metal complex represented by the formulawherein each R is a saturated aliphatic or aromatic hydrocarbon radical,including alkoxyand halo-suband stituted radicals, having up to 20carbon atoms; Q is phosphorus, arsenic, or antimony; R is hydrogen or R;R is a divalent saturated aliphatic or aromatic hydrocarbon radicalhaving up to 20 carbon atoms; R is a divalent saturated or ethylenicallyunsaturated hydrocarbon radical having from 3 to 10 carbon atoms; R ishydrogen or a methyl radical; R is an aromatic, saturated aliphatic, orethylenically unsaturated aliphatic hydrocarbon radical having up to 20carbon atoms; 11 is 0, 1, 2, or 3; m is 1 or 2; n is -5; e is 1-5, f is1 or 2; g is l-6; and the number of (L) and Z groups present in thecomplex is not greater than the number required for the metal to achievethe closed shell electronic configuration of the next higher atomicnumber inert gas; and x is a number representing the polymeric state ofthe complex which is 1, 2 or 3; and

(b) an aluminum-containing adjuvant selected from (2) a mixture of (1)compounds,

(3) a mixture of one or more R AlX or AlX compounds with one or morecompounds represented by the formula R M X or (4) an AlX compoundwherein each R is as defined above; each X is a halogen, each M is ametal of Group I-A, II-A, II-B, or III-A; each R is selected fromhydrogen or R; a is 1, 2 or 3, b is 0, 1 or 2, the sum of a and 'b being3; c is 1, 2 or 3, d is 0, 1 or 2, the sum of c and d being equal to thevalence of M 2. The process of claim 1 wherein the (a) component of thecatalyst is formed by admixing under catalyst formation conditions acopper, silver or gold containing salt of an organic acid having up to20 carbon atoms or a salt of an inorganic acid with at least one of said(L).

3. A process according to claim- 1 wherein the olefin hydrocarbon isselected from the group consisting of (1) acyclic monoolefins, includingthose with aryl, cycloalkyl, and cycloalkenyl substituents, having 3 toabout 20 carbon atoms per molecule, with no branching closer to thedouble bond than the 3-position and no quaternary carbon atom oraromatic substitution closer to the double bond than the 4-position, andmixtures of such unsubstituted acyclic monoolefins;

(2) a mixture of ethylene and one or more acyclic,

unsubstituted, internal monoolefins of (1);

(3) acyclic, nonconjugated polyenes having 5 to about 20 carbon atomsper molecule, containing 2 to about 4 double bonds per molecule andhaving at least one double bond with no branching nearer to it than the3-position and no quaternary carbon atom nearer to it than the4-position, and mixtures of such polyenes;

(4) a mixture of ethylene and one or more acyclic polyenes of (3) whichcontains at least one internal double bond;

(5) cyclopentene;

(6) cyclic and bicyclic monoolefins having 7 to about 12 ring carbonatoms, including those substituted with up to 3 alkyl groups having upto about 5 carbon atoms each with no branching closer to the double bondthan the 3-position and with no quaternary carbon atoms closer to thedouble bond than the 4-position;

(7) a mixture of one or more monocyclic olefins of (6) with ethylene orwith one or more unsubstituted, acyclic monoolefins of 1);

(8) cyclic and bicyclic nonconjugated polyenes having 5 to about 12 ringcarbon atoms including those substituted with up to 3 alkyl groupshaving up to 5 carbon atoms each, with at least one of the double bondshaving no branching closer than the 3-position and no quaternary carbonatom closer than the 4-position;

12 (9) a mixture of one or more monocyclic polyenes of 8) with one ormore acyclic l-olefins having from 2 to about 10 carbon atoms with nobranching closer to the double bond than the 3-position and noquaternary carbon atom closer to the double bond than the 4-position;and (10) polar group-substituted olefinic compounds of classes (1)through (9) containing from about 5 to 20 carbon atoms per molecule inwhich the polar group is no closer to the double bond than the5-position, and mixtures with unsubstituted members of 1).

4. The process of claim 3 wherein the feed olefin hydrocarbon isheptene-Z or pentene-2,

5. The process of claim 4 wherein the (a) component is(triphenylphosphine) Cu Cl and the (b) component is methylaluminumsesquichloride or ethylaluminum dichloride.

6. The process of claim 4 wherein the (a) component is(triphenylphosphine)AuCl and the (b) component is methylaluminumsesquichloride.

7. The process of claim 4 wherein the (a) component is[(triphenylphosphine)AgBr] and the (b) component is ethylaluminumdichloride, wherein at is 1, 2, or 3.

8. The process of claim 1 wherein the conversion according to the olefinreaction, as defined herein, can be visualized as comprising thereaction between two first pairs of carbon atoms, the two carbon atomsof each first pair being connected by an olefinic double bond, to formtwo new pairs from the carbon atoms of said first pairs, the two carbonatoms of each said new pairs being connected by an olefinic double bond.

9. The process of claim 1 wherein the conditions for the olefin reactioninclude a temperature in the range of from about -30 to about C., apressure which is sufficient to maintain the liquid phase, a time ofcontact in the range of from 0.1 to about hours, and a ratio of catalystcomposition to olefin feed of from about 0.001 to 100 millimoles ofcopper, silver or gold for each mole of olefin feed.

10. The proces of claim 1 wherein the conversion is accomplished in thepresence of an inert diluent in which both of the (a) and (b) componentsof the catalyst are at least partially soluble.

11. The process of claim 1 wherein the catalyst further includes a solidinorganic or organic support or carrier selected from the groupconsisting of silica, alumina, silica-alumina, titania, boria, zeolites,ion exchange resins, a solid polymer of 4-vinylpyridine and a solidpolymer of vinyl dimethylphosphine.

References Cited UNITED STATES PATENTS 2,993,035 7/1961 Christman252-429 A 2,993,942 7/ 1961 White et a1 252-429 B 2,989,516 6/1961Schneider 252-429 B 3,000,837 9/1961 Brachman 252-429 A 3,054,754 9/1962Lasky 252-429 B 3,117,938 1/ 1964 Burrus et al 252-431 N 2,792,3345/1957 Meguerian 252431 C 3,267,076 8/1966 Ishii et al 252-431 R3,448,140 6/ 1969 Gamlen et al 252-431 R 3,450,732 6/1969 Wilke et al.252-431 R 3,409,681 11/1968 Kroll 260-683.2

DELBERT E. GANTZ, Primary Examiner C. E. SPRESSER, JR., AssistantExaminer 'U.S. Cl. X.R.

260-94.9 B, 648 R, 649 R, 658 R, 666 A, 668 R, 677 R, 680 R

